TY - JOUR
T1 - Synthesis, structure, reactivity and photoluminescence of lanthanide(III) monoporphyrinate complexes
AU - WONG, Rick W K
AU - ZHU, Xunjin
AU - WONG, Wai Yeung
N1 - Funding Information:
We thank the Hong Kong Baptist University (FRG/03-04/11-52, FRG/05-06/II-03) and the Hong Kong Research Grants Council (HKBU 2023/00P, HKBU 2021/03P) for financial support.
PY - 2007/9
Y1 - 2007/9
N2 - A series of cationic lanthanide(III) monoporphyrinate complexes of the general formula [Ln(Por)(H2O)3]Cl (Ln = Yb3+ and Er3+; Por = porphyrinate dianion) were prepared via the protonolysis of Ln(NR2)3 with porphyrin free bases (H2Por). An unexpected neutral oxalate-bridged Yb porphyrinate dimer [Yb(Por)(DME)]2(μ-η2:η2-O2CCO2) was isolated and structurally characterized by X-ray crystallography when the protonolysis was carried out in an atmosphere of carbon dioxide. The coordinated aqua molecules of the cationic porphyrinate complexes are very labile and can be easily displaced by good donor solvents such as DMF or anionic tripodal ligand L2X- (L2X- = LOMe- and TpH-) to form the neutral complex [Ln(Por)(Cl)(DMF)2] or [Ln(Por)(L2X)], respectively. [Yb(Por)(H2O)3]Cl underwent dimerization to give the dimer [Yb(Por)(μ-OH)(H2O)]2 when dissolved in basic solution and [Yb(Por)(μ-Cl)(H2O)]2 in dilute HCl solution. Furthermore, [Yb(Por)(H2O)3]Cl behaves as a living catalyst for the cyclotrimerization of phenyl isocyanate to l,3,5-triphenyl-s-triazin-2,4,6-trione. Photoluminescence studies showed that the porphyrinate dianion, acting as an antenna, sensitized Ln3+ (Ln3+ = Nd3+, Er3+ and Yb3) ion emission in the near-infrared region, and that [Ln(TDPAPP)(LOMe)] complexes exhibited excellent optical limiting capability. Protonolysis of Ln(NR2)3 with N-confused porphyrin free bases (H2NCP) followed by the addition of the encapsulating tripodal anion, LOMe, gave lanthanide(III) N-confused porphyrinate complexes of the general formula [Ln(NCP)(LOMe)] (Ln = Yb3+ and Er3+; NCP = N-confused porphyrinate dianion), whose X-ray structures revealed an η2 agostic interaction between the metal center and the inner C-H bond of the NCP ligand.
AB - A series of cationic lanthanide(III) monoporphyrinate complexes of the general formula [Ln(Por)(H2O)3]Cl (Ln = Yb3+ and Er3+; Por = porphyrinate dianion) were prepared via the protonolysis of Ln(NR2)3 with porphyrin free bases (H2Por). An unexpected neutral oxalate-bridged Yb porphyrinate dimer [Yb(Por)(DME)]2(μ-η2:η2-O2CCO2) was isolated and structurally characterized by X-ray crystallography when the protonolysis was carried out in an atmosphere of carbon dioxide. The coordinated aqua molecules of the cationic porphyrinate complexes are very labile and can be easily displaced by good donor solvents such as DMF or anionic tripodal ligand L2X- (L2X- = LOMe- and TpH-) to form the neutral complex [Ln(Por)(Cl)(DMF)2] or [Ln(Por)(L2X)], respectively. [Yb(Por)(H2O)3]Cl underwent dimerization to give the dimer [Yb(Por)(μ-OH)(H2O)]2 when dissolved in basic solution and [Yb(Por)(μ-Cl)(H2O)]2 in dilute HCl solution. Furthermore, [Yb(Por)(H2O)3]Cl behaves as a living catalyst for the cyclotrimerization of phenyl isocyanate to l,3,5-triphenyl-s-triazin-2,4,6-trione. Photoluminescence studies showed that the porphyrinate dianion, acting as an antenna, sensitized Ln3+ (Ln3+ = Nd3+, Er3+ and Yb3) ion emission in the near-infrared region, and that [Ln(TDPAPP)(LOMe)] complexes exhibited excellent optical limiting capability. Protonolysis of Ln(NR2)3 with N-confused porphyrin free bases (H2NCP) followed by the addition of the encapsulating tripodal anion, LOMe, gave lanthanide(III) N-confused porphyrinate complexes of the general formula [Ln(NCP)(LOMe)] (Ln = Yb3+ and Er3+; NCP = N-confused porphyrinate dianion), whose X-ray structures revealed an η2 agostic interaction between the metal center and the inner C-H bond of the NCP ligand.
KW - Cationic lanthanide monoporphyrinate complexes
KW - Lanthanide porphyrinate dimers
KW - Metal-catalyzed cyclotrimerization
KW - N-Confused porphyrin
KW - Near-infrared sensitization
KW - Optical limiting property
UR - http://www.scopus.com/inward/record.url?scp=34548536665&partnerID=8YFLogxK
U2 - 10.1016/j.ccr.2006.11.014
DO - 10.1016/j.ccr.2006.11.014
M3 - Review article
AN - SCOPUS:34548536665
SN - 0010-8545
VL - 251
SP - 2386
EP - 2399
JO - Coordination Chemistry Reviews
JF - Coordination Chemistry Reviews
IS - 17-20
ER -